Ester and method of making same



Patented Nov. 16, 1943 2,334,389 ESTER AND METHOD OF MAKING SAME Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Ltd. Del., a corporation of Delaware Wilmington,

No Drawing. Original application June 25, 1941,

Divided and this application November 6, 1942, Serial No. 464,930

6 Claims. (Cl. 260-400) Serial No. 399,728.

This invention relates to a new chemical product or compound and to the manufacture of same, my present application being a division of my co-pending application Serial No. 399,728, filed June 25, 1941, which subsequently matured as U. S. Patent No. 2,305,067, dated December 15,1942.

One object of my invention is to provide a new chemical product or compound that isparticularly adapted for use as a demulsifier, in the resolution of crude oil emulsions.

Another object is to provide a practicable method for manufacturing said new chemical product or compound.

Although one of the primary objects of my invention is to provide a new compound or composition of matter that is an efficient demulsifier for crude oil emulsions of the water-in-oil type, the said compound or composition of matter may be employed in other arts, as hereinafter indicated. It also may have additional uses in various other fields which have not yet been investigated.

Attention is directed to U. S. Patent No. 2,184,794, dated December 26, 1939, to Melvin De Groote. Said patent is concerned with an ester, particularly a water-soluble ester of the following composition:

11 son-i in which X and Y are selected from the group consisting of hydrogen atoms; and

Lododcoozwnn j with what appears in aforementioned U. S. Patent No. 2,184,794, in substantially the following language:

"It is obvious that the radicals employed to replace the carboxylic hydrogen atom or atoms of maleic acid must contain at least one residual hydroxyl and preferably two. For this reason, it is evident that various'other materials are the functional equivalent of glycerol. For instance, ethylene glycol, propylene glycol, diglycerol, triglycerol, polyglycerol, variou glycols in which the ether linkage appears, such as diethylene glycol, etc. It is also obvious that glycerol chlorhydrin or some other similar chlorhydrin or some oxide such as glycidol, also would be the functional equivalent of glycerol.

The products described in said aforementioned patent are derived from triricinolein (caster oil) and are water-soluble. Indeed, they show colloidal water solubility beyond the range in which surface-active agents are ordinarily employed. For instance, surface-active agents may be employed in concentrations as low as one part to 30,000, or perhaps as high as a few parts per hundred, depending upon the specific nature of the industrial application involved. Such variation in concentration may depend on whether one is concerned with demulsification of oil field emulsions of the water-in-oil typ or is conoerned with the formation of emulsions of the oil-in-water type. Oddly enough, I have discovered that if one products a variant, new species or sub-species, or a new analog of the type of material described in the aforementioned De Groote patent, which new compound is characterized by the presence of a long chain hydrophile group, such new variant or analog has some unlooked-for properties. All such variants or analogs are derivatives of triricinolein, specifically and without exception. These new properties cannot be co-related to water solubility, for the reason that water solubility of the type of material described in the aforementioned De Groote patent is more than ample for the purposes intended in said patent or related uses. It is more likely that the new variant herein contemplated as a new chemical compound or composition of matter owes its improved quality to the manner in which the introduction of the long chain hydrophile group or groups alter its H /SOM OOC.C11H!:.O [ociicoowimonn] particularly oil-water OOC.C11H|:.O [Y] in which 112 is a small whole number varying from 7 through 17, and X and Y are selected from the group consisting of hydrogen atoms:

Loo-.iicoozwn radicals, one obtains a particularly valuable new compound or composition of matter. The various symbols have their prior significance. Subsequently certain further modifications will be described. In essence, glycerol as a reactant in the procedure described in U. S. Patent No. 2,184,- 794, as far as combination with sulfosuccinic acid radicals is concerned, is replaced by a polyethylene glycol of the kind exemplified by heptaethylene glycol, octaethylene glycol, nonaethylene glycol, to and including heptadecylene glycol. In this connection, attention is directed to the fact that the aforementioned patent contemplates the use of various glycols in which the ether linkage appears, such as diethylene glycol. I have found, however, that the property of the type of compound herein contemplated is not significantly different from those in the aforementioned United States patent, when the ether linkage occurs only one time, or two or three times, for instance, as when diethylene glycol is used as a reactant in the manufacture of such compounds, instead of glycerol; but it does change enormously when one employs long chain glycols in which the ether linkage recurs a large number of times;

for example, as when one employs nonaethylene glycol or the like.

As far as I am aware, in view of what has been said previously, this marked enhancement in valuable properties, particularly in respect to certain industrial applications, is entirely unpredictable. Said aforementioned U. S. Patent No. 2,184,794 makes reference, in turn, to U. 8. Patent No. 2,028,091, dated January 14, 1936, to Jaeger. Said Jaeger patent is concerned with a broad genus in which various hydroxylated bodies may be combined with a carboxyl radical of sulfosuccinic acid; for instance, such sulfo acid may be combined with octyl alcohol, capryl alcohol, tetrahydrofurfural alcohol, and the like. The present invention is not concerned with such esters in which such other radicals or groups appear. The peculiar advantage herein noted appears only in such instances where the triricinolein radical and the polyalkylene glycol radical of the kind hereinafter described appear jointly in the same molecule. Invention is strictly so limited; and as far as I am aware, the introducthe manufacture of these products from gly ro or the like; and since nonaethylene glycol and similar products are commercially available, it hardly appears necessary to describe the product and the method of manufacture of the same, al-

though this will be done purely as a matter of convenience.

Briefly, then, my present invention relates to new esters derived from sulfosuccinic acid by esterification of one carboxylic hydrogen atom by means of triricinolein; and the other carboxylic hydrogen atom by means of a'polyalkylene glycol of the kind described, in such a manner that there is present a residual hydroxyl radical attached to the glycol residue; the ester is furthermore characterized by the fact that the sulfonic hydrogen atom is replaced by a metallic atom, an ammonium radical, or an amine radical, including an alkylolamine radical, or any salt-forming cation. The peculiar combination of two such widely dissimilar alcoholic bodies with sulfodicarboxylic acids, presents certain remarkable properties, due to unexpected co-operation between these dissimilar alcoholic radicals, i. e., the triricinolein radical and the polyalkylene glycol radical, as previously suggested. A further part of the present invention consists in the particular method or procedure employed in the manufacture or synthesis of the compound or compounds herein contemplated. Reference has already been made to some uses of materials of the kind herein contemplated in thevarious arts. Additionally, such materials may be used as substitutes for soaps, Turkey red oils, sulfonated alcohols, and the like. They are particularly valuable as emulsifying agents, washing agents, dispersing agents,

etc. As to other possible uses, see Chemical Industries," 48, 3246 (1941). Specific reference has already been made to the use of these compounds or compositions as demulsifying agents for crude oil emulsions of the water-in-oil type.

In referring to polyethylene glycols as reactants for the introduction of th desired polyalkylene glycol radical, it is to be noted that the polypropylene glycols or polybutylene glycols could also be employed. Thus, for convenience, in the broadest aspect the polyalkylene glycols employed may be indicated by the following formula:

OH (CnHznO) 112K in which m has its previous significance and n represents a numeral varying from 2 to 4.

As far as the range of oxyalkylated compounds employed as reactants is concerned, it is my preference to employ those having approximately 8-12 oxyalkylene groups, particularly 8-12 oxyethylene groups. The preference to use the oxyethylated compounds is due, in part, to the fact that they are commercially available, and particularly so in two desirable forms. The most desirable form is the so-called nonaethylene glycol, which, although consisting largely of nonaethylene glycol, may contain small amounts of heptaethylene and octaethyleneglycols, and possibly minor percentages of the higher homologs.-

particularly a polyethylene formed;

ing a sharper separation on a commercial scale; and it is understood that mixtures of one or more of the glycols may be employed, as well as a single glycol. As pointed out, it is particularly preferred-to employ nonaethylene glycol as commercially available, although it is understood that this product contains other homologs, as indicated.

Substantially as desirable as the upper distillable polyethylene glycols, are the lower non-distlllable polyethylene glycols. These materials are available in the form of a waxy water-soluble material, and the general range may vary somewhat from decato tetradecaethylene glycol. As is well understood, the method of producing such glycols would cause some higher homologs to be and thus, even in this instance, there may be present some oxyethylene glycols within the higher range above indicated. One need not point out that these particular compounds consist of mixtures, and that in some instances, particularly desirable esters are obtained by making mixtures of the liquid. nonaethylene glycol with the soft, waxy, lower non-distillable polyethylene glycols. For the sake of convenience, reference in the examples will be to nonaethylene glycol; and calculations will be based on a theoretical molecular weight of 414. Actually, in manufacture, the molecular weight or the glycol employed, whether a higher distillable polyethylene glycol, or a lower non-distillable polyethylene glycol, or a mixture of the same, should be determined and reaction conducted on the basis of such determination, particularly in conjunction with the hydroxyl or acetyl value.

If castor oil or triricinolein is esterified with a mole of maleic anhydride untilone carboxyl disappears, the composition of the product is as follows:

where R. designates the ricinoleic acid nucleus or residue. If this product is then treated with a mole of a polyalkylene glycol of the kind previously described, the composition then becomes as follows:

H .oocxvon mdoocm'on If this material i then treated with sodium bisulphite, for example, the resulting product becomes:

l Na H S:

Naturally, instead of using one mole of maleic anhydride, one could employ two moles of maleic anhydride, followed by the use of two moles of the selected glycol; or, if desired, one could use three moles of maleic anhydride, followed by the use of three moles of glycol. If two moles of maleic anhydride were used, one would necessarily employ two moles of sodium blsulflte or its equivalent. Similarly, if one employed three moles of maleic anhydride, one would employ three moles of sodium blsulflte or the like.

It is understood, of course, that a polymaleated triricinolein may be esterlfled by employing one mole or a poiyalkylene lycol or the kind described, and one mole of some other polyhydric alcohol, for instance, glycerol or diethylene glycol.

The manufacture of monomaleated, dimaleated, and trimaleated triricinolein is well known. There is no dimeulty in obtaining either the monomaieated or dimaleated product; but it is somewhat diflicult to convert completely triricinolein into the trimaleated product. Generally speaking, one is more apt to obtain a mixture containing some trimaleated triricinolein, and some dimaleated triricinolein.

The new chemical compound or product that constitutes my present invention, is prepared by treating one mole of triricinolein in the form of castor oil with two moles of maleic anhydride at a relatively low temperature, for instance, 140 C., or thereabouts; until one obtains a product having only one hydroxyl and having two free carboxylic radicals. Generally speaking, it the temperature of esteriflcation is held reasonably low, one finds that when the product indicates the proper acid value (1. e., the existence of two free carboxyl radicals), it will automatically have the proper hydroxyl or acetyl value.

Such product can then be converted into various specific examples. by means of procedures such as the following:

Intermediate product, Example 1 One pound mole of dimaleated triricinolein is esterifled with two pound moles of nonaethylene glycol at approximately 140 C. until the acid value disappears completely, and the product shows the proper acetyl or hydroxyl value. Needless to say, if the temperature is properly controlled and the fractional ester has been suitably prepared, then when the acid value disappears completely, the product will have the proper hydroxyl or acetyl value. Dried carbon dioxide, or some other dried inert gas, may be employed to hasten esteriflcation. Esterification is also hastened at times by the presence of a comparatively minute amount of a sulfonic acid. Dried hydrochloric acid gas may also be employed.

Intermediate product, Example 2 A mixture of lower non-dlstillable polyethylene glycols representing approximately decato tetradeca-ethylene glycol, is substituted for nonaethylene glycol in the preceding example.

Intermediate product, Example 3 A 50-50 mixture of nonaethylene glycol and lower non-distillable polyethylene glycols of the kind described in the previous example is sub-' stituted for nonaethylene glycol in Example 1.

Intermediate product, Example 4 glycerol.

Intermediate product, Example 5 7B radicals into the ester.

Intermediate product, Example 6 inorganic bisulfite present, or at the most, only insignificant percentages, with the result that one obtains a material which is readily watersoluble, even in relatively small amounts, such as less than 1%. Needless to say, the reaction is not limited to sodium bisulfite, but one may employ any functional equivalent, for instance, potassium bisulfite, amylamine bisulfite, ethanolamine bisulfite, diethanolamine bisulfite, triethanolamine bisulfite, morpholine bisulfite, cyclohexylamine bisulfite, benzylamine bisulfite, etc. Oneprocedure commonly employed is to add a suitable basic material to the ester insuch a manner as to prevent saponification and then pass in sulfur dioxide gas.

Needless to say, maleic acid, of course, can replace maleic anhydride in the procedure previously described for manufacturing the new composition of matter herein contemplated. The same is true of the corresponding acyl halide, such as maleyl chloride. It is further obvious that nonaethylene glycol monomaleate or the like could be employed to act as a combined equivalent of both maleic anhydride and nonaethylene glycol or its equivalent. Sulfosuccinic acid sodium salt, if available, could, of course, act as a substitute for both sodium bisulfite and maleic anhydride or maleic acid. Similarly, nonaethylene glycol ester of sodium sulfosuccinic acid could be employed as a combined substitute for sodium bisulfite, maleic anhydride, and nonaethylene glycol. There may be other obvious equivalents which would be perfectly apparent to a skilled chemist; and no further elaboration is required. As far as the new chemical compounds or compositions of matter which constitute the present invention are concerned, it is immaterial what particular pro cedure or method is employed to manufacture the same. Wherever available, naturally isomeric forms of the various compounds may be employed. The compounds herein contemplated may be manufactured in the manner herein described, or may be manufactured by any suitable process.

In the hereto appended claims, it is understood that wherever an ionizable hydrogen atom of a sulfonic radical has been replaced by the metallic sodium atom, that ammonium radicals, amine radicals, other metallic atoms, etc. are the functional equivalents thereof. Similarly, in the appended claims, wherever reference to a glycerol radical, or rather, to a dihydroxy propyl radical,

appears, it is understood that any similar radical having at least one free hydroxyl, even though it be of an alkyl-oxy-alkyl nature (i. e., containing an ether linkage), rather than simply an alkyl radical, is also the functional equivalent thereof. Various radicals of this type have been enumerated previously.

In the hereto attached claims it is intended (OHaCi'II-IMCOO) aCaHa As has been pointed out, materials of the kind herein contemplated may find uses as wetting, detergent, and leveling agents in the laundry, textile, and dyeing industry; as wetting agents and detergents in the acid washing of fruit, in the acid washing of building stone and brick; as a wetting agent and spreader in the application of asphalt in road building and the like, as a constituent of soldering flux preparations; as a flotation reagent in the flotation separation or various minerals; for flocculation and coagulation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifiers for cosmetics, spray oils, water-repellent textile finish, etc. eighaustlve.

However, the most important phase of the present invention, as far as industrial application goes, is concerned with the'use of the mapounds or reagents herein employed as demulsiflers may also be used for other purposes, for instance, as a break inducer in doctor treatment of the kind intended to sweeten gasoline. See U. S. Patent No. 2,157,223, dated May 9, 1939, to Sutton.

Chemical compounds of the kind herein described are also bearing strata by means of strong mineral acid, such as hydrochloric acid. Similarly, some members are effective as surface tension depressants or wetting agents in the flooding of exhausted oil-bearing strata.

A somewhat analogous use is in the removal of a residual mud sheath which remains after drilling a well by the rotary method. Sometimes the drilling mud contains added calcium carbonate expedite its removal.

As to using compounds of the kind herein described as flooding agents for recovering oil from subterranean strata, reference is made to the procedure described in detail in U. S. Patent No. 2,226,119, dated December 24, 1940, to De Groote and Keiser. As to using compounds of the kind herein described as demulsifiers, or in particular as surface tension depressants, in combination with mineral acid or acidization of oil-bearing strata, reference is made to U. S. Patent No. 2,233,383, dated February 25, 1941, to De Groote and Keiser.

It may be well to emphasize once more that the compounds herein contemplated, although most desirably obtained from polyethylene glycols, may also be obtained from butyiene or propylene glycols, in which the ether linkage appears at Those obtained from of the kind described, however, are enormously These uses are by no means in which M is selected from the group consisting of a metallic atom, an ammonium radical, and an amine radical; m is a small whole number varying from '7 through 1'7; n is a numeral from 2 to 4; and X and Y are selected from the group consisting of hydrogen atoms,

11 808M 5 00. I oooo(o..'m..;o).11

H 801M [0 (M 3060 O.Z(0H) ,1

and

'radicals, in which Z(0H)1| is a polyhydric alcohol residue, and n is a small whole number which is at least 1.

2. A water-soluble ester of the following composition:

egg-o O G.CuHu.O [X] H SOiM [061 060 0 (ClHCQ) nH] 'and 1: /BOM [ooiiooozmmii radicals, in which mom, is a polyhydric alcohol residue, and n is a small whole number which is at least 1.

3. A water-soluble ester of the following composition:

a SOIM cmuooowim] [ooocx icoowmloym] H a where M is selected from the group consisting of a metallic atom, an ammonium radical, and an amine radical; and m is a small whole number varying from '7 through 17.

4. A water-soluble ester of the following composition:

11 803M [onwnrrucoonoinll [oooooooowirnohn] t 2 where M is selected from the group consisting of a metallic atom, an ammonium radical, and an amine radical; and m is a small whole number varying from 7 through 17.

5. A water-soluble ester of the following composition:

a soiM [(OH)$(Ci1Ha2COO)aCsHs] [ooot wcoowmlonn] where M is selected from the group consisting of a metallic atom, an ammonium radical, and an amine radical; and m is a small whole number varying from '7 through 17.

6. A method of producing an ester as defined in claim 1, which comprises reacting triricinolein with a compound containing a labile maleyl radical, and selected from the class consisting of maleic acid, maleic anhydride, and maleyl chloride, to produce an ester, and in the molecular proportions calculated to give the corresponding acid ester, and then reacting this resulting fractional ester with nonc-aethylene glycol in amounts to produce the neutral ester, followed by sulfonation with a bisulflte.

MELVIN DE GROOTE. 

